EP3438233A1 - Composition d'huile lubrifiante et réducteur de précision l'utilisant - Google Patents

Composition d'huile lubrifiante et réducteur de précision l'utilisant Download PDF

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Publication number
EP3438233A1
EP3438233A1 EP17775550.1A EP17775550A EP3438233A1 EP 3438233 A1 EP3438233 A1 EP 3438233A1 EP 17775550 A EP17775550 A EP 17775550A EP 3438233 A1 EP3438233 A1 EP 3438233A1
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Prior art keywords
lubricating oil
oil composition
mass
group
compound
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Granted
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EP17775550.1A
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German (de)
English (en)
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EP3438233A4 (fr
EP3438233B1 (fr
Inventor
Takuya Ono
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
    • C10M137/105Thio derivatives not containing metal
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M139/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02Well-defined aliphatic compounds
    • C10M2203/024Well-defined aliphatic compounds unsaturated
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024Propene
    • C10M2205/0245Propene used as base material
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/2805Esters used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/041Triaryl phosphates
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/047Thioderivatives not containing metallic elements
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/12Groups 6 or 16
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/06Instruments or other precision apparatus, e.g. damping fluids

Definitions

  • the present invention relates to a lubricating oil composition, and a precision reduction gear using the same.
  • a lubricating oil composition for use for reduction gears of various industrial machines is required to have wear resistance for preventing wear of gears, etc.
  • a method for improving wear resistance of a lubricating oil in general, there are known a method of adding a phosphorus-sulfur-containing compound and a sulfur-containing compound to a lubricating oil (for example, see PTL 1), a method of adding a sulfur-based compound, an organic molybdenum-based compound and a phosphorus-containing compound (for example, see PTL 2), etc.
  • a method for reducing a friction coefficient in general, there is known a method of adding an organic molybdenum-based compound (for example, see PTL 3).
  • precision reduction gears are incorporated in joint sites and the like of industrial robots.
  • Such precision reduction gears use a specific gear such as a planetary gear for realizing a large reduction ratio in a limited space, and the gear ratio of engaging gears (number of rack gear teeth/number of pinion gear teeth) therein is extremely large.
  • industrial robots repeat switchover of reciprocating motion and motion speed. Accordingly, precision reduction gears for industrial robots are given an extremely larger load than that to general reduction gears. Consequently, an oil film is difficult to form in the lubrication state, therefore often resulting in boundary lubrication or mixed lubrication in many cases, and causing wear with ease to form wear debris.
  • a conventional lubricating oil heretofore used in reduction gears of various industrial machines could not still attain sufficient wear resistance even though the above-mentioned compounds are added thereto.
  • the friction coefficient could not be still sufficiently reduced even by the addition of the above-mentioned compounds.
  • an object of the present invention is to provide a lubricating oil composition capable of exhibiting excellent wear resistance in a wide range of contact pressures ranging from high to low and having a low friction coefficient, and to provide a precision reduction gear using the lubricating oil composition.
  • the present invention provides the following [1] to [3].
  • a lubricating oil composition capable of exhibiting excellent wear resistance in a wide range of contact pressures ranging from high to low and having a low friction coefficient, and a precision reduction gear using the lubricating oil composition.
  • the lubricating oil composition of the present invention contains a base oil, a thiophosphate compound (A) represented by the general formula (I) and a molybdenum-based compound (B).
  • the lubricating oil composition of one embodiment of the present invention further contains a phosphate compound (C) not containing a sulfur atom.
  • the lubricating oil composition of one embodiment of the present invention further contains a sulfur-based compound (D) containing 2 or more sulfur atoms in the molecule and not containing a phosphorus atom.
  • the lubricating oil composition of one embodiment of the present invention may contain any other additive for a lubricating oil than the above-mentioned components (A) to (D), for example, an antioxidant (E), within a range not detracting from the advantageous effects of the present invention.
  • the total content of the base oil, the component (A) and the component (B) is, based on the total amount of the lubricating oil composition, preferably 60.01% by mass or more, more preferably 70.01% by mass or more, even more preferably 80.01% by mass or more, further more preferably 85.01% by mass or more, especially preferably 90.01% by mass or more, and is generally 100% by mass or less, preferably 99.9% by mass or less, more preferably 99% by mass or less.
  • the total content of the base oil and the components (A) to (E) is, based on the total amount of the lubricating oil composition, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 85 to 100% by mass, further more preferably 90 to 100% by mass, especially preferably 95 to 100% by mass.
  • the base oil for use in the lubricating oil composition of one embodiment of the present invention may be at least one selected from mineral oils and synthetic oils that are used in ordinary lubricating oils.
  • mineral oil examples include atmospheric residues obtained through atmospheric distillation of crude oils, or mineral oils obtained from lubricating oil fractions that are obtained through reduced pressure distillation of atmospheric residues obtained through atmospheric distillation of crude oils, in one or more treatments of solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing or hydrorefining; and wax-isomerized mineral oils; mineral oils obtained according to a method of isomerization of GTL (GTL is an abbreviation of gas to liquids) wax such as Fischer-Tropsch wax.
  • GTL is an abbreviation of gas to liquids wax
  • Fischer-Tropsch wax is an abbreviation of gas to liquids wax
  • the synthetic oil examples include aliphatic hydrocarbon oils (polyolefin-based synthetic oils) such as poly- ⁇ -olefins (PAO), ethylene- ⁇ -olefin copolymers, and polybutenes; aromatic hydrocarbon oils such as alkylbenzenes, and alkylnaphthalenes; glycol oils such as polyalkylene glycols; ether oils such as polyphenyl ethers, and alkyl-substituted diphenyl ethers; ester oils such as polyol esters, dibasic acid esters, and carbonates; silicone oils; fluorinated oils; and GTL.
  • polyolefin-based synthetic oils such as poly- ⁇ -olefins (PAO), ethylene- ⁇ -olefin copolymers, and polybutenes
  • aromatic hydrocarbon oils such as alkylbenzenes, and alkylnaphthalenes
  • glycol oils such as polyalkylene glycols
  • ester oils and polyolefin-based synthetic oils are preferred among these synthetic oils; poly- ⁇ -olefins (PAO), ethylene- ⁇ -olefin copolymers, polyol esters, dibasic acid esters, carbonates and GTL are more preferred; and poly- ⁇ -olefins (PAO) are even more preferred.
  • the base oil may be a single system using one kind of the above-mentioned mineral oils and synthetic oils, or may be a mixed system of two or more kinds of mineral oils, a mixed system of two or more kinds of synthetic oils, or a mixed system of one or more of mineral oils and synthetic oils.
  • the base oil for use in the lubricating oil composition of one embodiment of the present invention is preferably one containing a mineral oil belonging to Group II or III in base oil grouping by API, or one containing a synthetic oil, and is more preferably one containing a synthetic oil.
  • the kinematic viscosity at 40°C (hereinafter may be referred to as "40°C kinematic viscosity") of the base oil for use in the lubricating oil composition of one embodiment of the present invention is, from the viewpoint of lubricity, cooling performance and friction loss reduction in stirring, preferably 40 mm 2 /s or more.
  • the kinematic viscosity at 40°C of the base oil is preferably 10 mm 2 /s or more, and 1800 mm 2 /s or less, more preferably 40 mm 2 /s or more and 1650 mm 2 /s or less, even more preferably 50 mm 2 /s or more and 1,500 mm 2 /s or less, further more preferably 60 mm 2 /s or more and 1,200 mm 2 /s or less, especially more preferably 70 mm 2 /s or more and 1,100 mm 2 /s or less.
  • the viscosity index of the base oil is, from the viewpoint of suppressing viscosity change with temperature change, preferably 60 or more, more preferably 75 or more, even more preferably 90 or more.
  • the base oil for use in the lubricating oil composition of one embodiment of the present invention is a mixture of two or more kinds of base oils
  • the 40°C kinematic viscosity and the viscosity index thereof each may fall within the above-mentioned range.
  • the kinematic viscosity and the viscosity index of the base oil and the lubricating oil composition are values measured according to JIS K2283.
  • the content of the base oil is, based on the total amount of the lubricating oil composition, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, further more preferably 85% by mass or more, especially more preferably 90% by mass or more, and is preferably 99.9% by mass or less, more preferably 99.0% by mass or less, even more preferably 98.0% by mass or less.
  • the lubricating oil composition of one embodiment of the present invention contains a thiophosphate compound (A) represented by the general formula (I).
  • the component (A) includes aryl thiophosphates, and alkylaryl thiophosphates.
  • R 1 , R 2 and R 3 each independently represent an aryl group having 6 to 12 ring carbon atoms, and the aryl group may be substituted with an alkyl group having 1 to 3 carbon atoms.
  • the aryl group represented by R 1 , R 2 and R 3 includes a substituted or unsubstituted phenyl group, a substituted or unsubstituted 1-naphthyl group, a substituted or unsubstituted 2-naphthyl group, and a substituted or unsubstituted biphenyl group.
  • one or more hydrogen atoms that the aryl group has may be substituted with an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • the position of the alkyl group may be, in the case where the aryl group is a phenyl group or a biphenyl group, any of an ortho-, para- or meta-position, and in the case where the aryl group is a naphthyl group, the position may be any of an ⁇ - or ⁇ -position.
  • the component (A) is preferably a thiophosphate compound (A1) represented by the following general formula (II).
  • R 4 , R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group, an n-proyl group and an isopropyl group.
  • the position of the substituents R 4 , R 5 and R 6 may be any of an ortho-, para- or meta-position.
  • the thiophosphate compound (A) represented by the general formula (II) includes tricresyl thiophosphate and triphenyl phosphorothioate.
  • one alone of the component (A) may be used or two or more kinds thereof may be used in combination.
  • the content of the component (A) is, based on the total amount of the lubricating oil composition, preferably 0.1% by mass or more and 1.0% by mass or less. More preferably, the content is 0.2% by mass or more and 0.8% by mass or less, even more preferably 0.3% by mass or more and 0.6% by mass or less.
  • a lubricating oil composition when the content of the component (A) is 0.1% by mass or more and 1.0% by mass or less based on the total amount of the lubricating oil composition, a lubricating oil composition can be provided which can have a low friction coefficient and have excellent wear resistance in a wide range of contact pressures ranging from high to low to such an extent that the composition can resist to lubrication conditions required for precision reduction gears to be incorporated in joint sites of industrial robots that are given an extremely large load and are readily worn to form wear debris.
  • the content of a thiophosphate compound represented by the following general formula (III) is preferably as small as possible.
  • the composition may rather cause formation of wear debris and could hardly improve wear resistance.
  • the content of the thiophosphate compound represented by the following general formula (III) is preferably 0 to 10 parts by mass, relative to 100 parts by mass of the component (A), more preferably 0 to 5 parts by mass, even more preferably 0 to 1 part by mass.
  • R 7 , R 8 and R 10 each independently represent a linear or branched, saturated or unsaturated aliphatic hydrocarbon group having 1 to 18 carbon atoms, or a saturated or unsaturated cyclic hydrocarbon group having 5 to 18 ring carbon atoms and optionally having a substituent.
  • R 9 represents a linear or branched alkylene group having 1 to 6 carbon atoms.
  • X 1 , X 2 and X 3 each independently represent an oxygen atom or a sulfur atom.
  • the content of a thiophosphate compound represented by the following general formula (IV) is preferably as small as possible.
  • the composition may rather cause formation of wear debris and could hardly improve wear resistance.
  • the content of the thiophosphate compound represented by the following general formula (IV) is preferably 0 to 10 parts by mass, relative to 100 parts by mass of the component (A), more preferably 0 to 5 parts by mass, even more preferably 0 to 1 part by mass.
  • R 11 , R 12 and R 13 each independently represent a linear or branched, saturated or unsaturated aliphatic hydrocarbon group having 4 or more carbon atoms (generally having 4 to 18 carbon atoms).
  • the position of the substituents R 11 , R 12 and R 13 may be any of an ortho-, para- or meta-position.
  • the lubricating oil composition of one embodiment of the present invention contains a molybdenum-based compound (B).
  • a molybdenum-based compound (B) an organic molybdenum compound heretofore used as an additive for a lubricating oil be used, and examples of the organic molybdenum compound include molybdenum carbamate, molybdenum dicarbamate, molybdenum dithiophosphate (MoDTP), and molybdenum dithiocarbamate (MoDTC).
  • MoDTP and MoDTC are preferred.
  • molybdenum dithiophosphate As the molybdenum dithiophosphate (MoDTP), compounds represented by the following general formula (b1-1) and compounds represented by the following general formula (b1-2) are preferred.
  • R 14 to R 17 each independently represent a hydrocarbon group, and these may be the same as or different from each other.
  • X 4 to X 11 each independently represent an oxygen atom or a sulfur atom, and these may be the same as or different from each other. However, at least one of X 4 to X 11 in the formula (b1-1) is a sulfur atom, and at least one of X 4 to X 7 in the formula (b1-2) is a sulfur atom.
  • X 4 and X 5 are oxygen atoms
  • X 6 to X 11 are sulfur atoms.
  • the molar ratio of sulfur atom to oxygen atom in X 4 to X 11 [sulfur atom/oxygen atom] is preferably 1/4 to 4/1, more preferably 1/3 to 3/1.
  • the molar ratio of sulfur atom to oxygen atom in X 4 to X 7 [sulfur atom/oxygen atom] is preferably 1/3 to 3/1, more preferably 1.5/2.5 to 2.5/1.5.
  • the carbon number of the hydrocarbon group that may be selected for R 14 to R 17 is preferably 1 to 20, more preferably 3 to 18, even more preferably 4 to 16, further more preferably 5 to 12.
  • examples of the hydrocarbon group that may be selected for R 14 to R 17 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group; an alkenyl group such as an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a t
  • the molybdenum dithiocarbamate includes a binuclear molybdenum dithiocarbamate having two molybdenum atoms in one molecule, and a trinulcear molybdenum dithiocarbamate having three molybdenum atoms in one molecule.
  • a binuclear molybdenum dithiocarbamate is preferred; and compounds represented by the following general formula (b2-1) and compounds represented by the following general formula (b2-2) are more preferred.
  • R 18 to R 21 each independently represent a hydrocarbon group, and these may be the same as or different from each other.
  • X 12 to X 19 each independently represent an oxygen atom or a sulfur atom, and these may be the same as or different from each other.
  • At least one of X 12 to X 19 in the formula (b2-1) is a sulfur atom.
  • X 12 and X 13 in the formula (b2-1) are oxygen atoms and X 14 to X 19 are sulfur atoms.
  • X 12 to X 15 in the formula (b2-2) are oxygen atoms.
  • the molar ratio of sulfur atom to oxygen atom in X 12 to X 19 [sulfur atom/oxygen atom] is preferably 1/4 to 4/1, more preferably 1/3 to 3/1.
  • the molar ratio of sulfur atom to oxygen atom in X 12 to X 15 [sulfur atom/oxygen atom] is preferably 1/3 to 3/1, more preferably 1.5/2.5 to 2.5/1.5.
  • the carbon number of the hydrocarbon group that may be selected for R 18 to R 21 is preferably 1 to 20, more preferably 3 to 18, even more preferably 4 to 16, further more preferably 5 to 12.
  • hydrocarbon group that may be selected for R 18 to R 21 are the same as those of the hydrocarbon group that may be selected for R 14 to R 17 in the formulae (b1-1) and (b1-2).
  • the component (B) in the lubricating oil composition of one embodiment of the present invention, one alone may be used for the component (B) or two or more kinds may be used in combination.
  • the component (B) MoDTP and MoDTC may be used in combination.
  • the ratio by mass of the component (A) to the component (B) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, even more preferably 3/7 to 7/3, further more preferably 4/6 to 6/4.
  • a lubricating oil composition when the ratio by mass of the component (A) to the component (B) falls within a range of 1/9 to 9/1, a lubricating oil composition can be provided which can have a low friction coefficient and have excellent wear resistance in a wide range of contact pressures ranging from high to low to such an extent that the composition can resist to lubrication conditions required for precision reduction gears to be incorporated in joint sites of industrial robots that are given an extremely large load and are readily worn to form wear debris.
  • the lubricating oil composition of one embodiment of the present invention further contains a phosphate compound (C) not containing a sulfur atom.
  • a triphosphate or acid phosphate compound is preferred, and a triphosphate or acid phosphate compound represented by the following general formula (c1) is more preferred.
  • R 22 represents a hydrocarbon group having 2 to 24 carbon atoms, and m represents 1, 2 or 3.
  • m represents 1, 2 or 3.
  • plural R 22 O's may be the same as or different from each other.
  • the hydrocarbon group having 2 to 24 carbon atoms represented by R 22 includes an alkyl group having 2 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, and an arylalkyl group having 7 to 24 carbon atoms.
  • the alkyl group having 2 to 24 carbon atoms and the alkenyl group having 2 to 24 carbon atoms may be linear, branched or cyclic, and examples thereof include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, various nonadecyl groups, various eicosyl groups, various heneicosyl groups, various docosyl groups, various tricosyl groups, various tetracosyl groups, a cyclopentyl group, a cyclohexyl group, an allyl group, a
  • Examples of the aryl group having 6 to 24 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.
  • Examples of the arylalkyl group having 7 to 24 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a methylbenzyl group, a methylphenethyl group, and a methylnaphthylmethyl group.
  • the phosphate compound represented by the general formula (c1) is preferably one having a hydrocarbon group having 2 to 18 carbon atoms.
  • lubricating oil composition of one embodiment of the present invention one alone may be used for the component (C) or two or more kinds may be used in combination. Further, amine salts and imide salts of these phosphate compounds may also be used.
  • the content thereof is, based on the total amount of the lubricating oil composition, preferably 0.05% by mass or more and 1.5% by mass or less, more preferably 0.08% by mass or more and 1.2% by mass or less, even more preferably 0.1% by mass or more and 1.0% by mass or less.
  • the content of the component (C) when the content of the component (C) is 0.05% by mass or more and 1.5% by mass or less, a lubricating oil composition having more excellent wear resistance in a wide range of contact pressures ranging from high to low can be provided.
  • the lubricating oil composition of one embodiment of the present invention further contains a sulfur-based compound (D) containing 2 or more sulfur atoms in the molecule and not containing a phosphorus atom (hereinafter may be referred to as "sulfur-based compound (D)").
  • a sulfur-based compound (D) containing 2 or more sulfur atoms in the molecule and not containing a phosphorus atom
  • the sulfur-based compound (D) is preferably one that is given a rating of 2 or less in a copper corrosion test (JIS K 2513) where the compound is added to the base oil to be contained in the lubricating oil composition of one embodiment of the present invention in an amount of 1% by mass and tested under the measurement condition of 100°C for 3 hours.
  • the sulfur-based compound (D) given a rating of 2 or less in the copper corrosion test can better heat resistance of the lubricating oil composition. More preferably, the rating in the copper corrosion test is 1.
  • the sulfur-based compound (D) is preferably an organic compound containing 2 or more sulfur atoms in the molecule and not containing a phosphorus atom, and preferred examples of the sulfur-based compound (D) include a dithiocarbamate compound.
  • the dithiocarbamate compound include an alkylenebisdialkyl dithiocarbamate. Above all, compounds having an alkylene group having 1 to 3 carbon atoms and an linear or branched, saturated or unsaturated alkyl group having 3 to 20 carbon atoms or a cyclic alkyl group having 6 to 20 carbon atoms are preferably used.
  • sulfur-based compounds (D) examples include methylenebis(dibutyldithiocarbamate), methylenebis(dioctyldithiocarbamate), and methylenebis(tridecyldithiocarbamate).
  • methylenebis(dibutyldithiocarbamate) is preferred.
  • lubricating oil composition of one embodiment of the present invention one alone may be used for the component (D) or two or more kinds may be used in combination.
  • the content thereof is, based on the total amount of the lubricating oil composition, preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.02% by mass or more and 0.5% by mass or less, even more preferably 0.05% by mass or more and 0.3% by mass or less.
  • a lubricating oil composition having more excellent wear resistance in a wide range of contact pressures ranging from high to low can be provided.
  • the content of the component (D) is 1% by mass or less based on the total amount of the lubricating oil composition, sludge formation may be prevented.
  • the lubricating oil composition of one embodiment of the present invention may contain, as needed, any other anti-wear agent, extreme-pressure agent and the like except the components (A) to (D) within a range not detracting from the advantageous effects of the present invention.
  • the content of the other anti-wear agent and extreme-pressure agent than the components (A) to (D) in the lubricating oil composition of one embodiment of the present invention is, relative to 100 parts by mass of the component (A), preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, even more preferably 0 to 1 part by mass.
  • lubricating oil composition of one embodiment of the present invention specifically, preferred examples of the combination of the above-mentioned constituent components are embodiments of the following ⁇ 1> to ⁇ 3>.
  • the lubricating oil composition of one embodiment of the present invention may contain, as needed, an antioxidant within a range not detracting from the advantageous effects of the present invention.
  • the lubricating oil composition of one embodiment of the present invention further contain an antioxidant (E).
  • antioxidant (E) a phenol-based antioxidant, an amine-based antioxidant and the like are preferably used.
  • the phenol-based antioxidant is not specifically limited, and for example, may be suitably selected any desired one from known phenol-based antioxidants heretofore used as an antioxidant for lubricating oil.
  • the phenol-based antioxidant include 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 4,4'-bis(2-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-isobutylidenebis(4,6-dimethylphenol), 2,2'-methylenebis(4-
  • amine-based antioxidant examples include monoalkyldiphenylamine-based antioxidants such as monooctyldiphenylamine, and monononyldiphenylamine; dialkyldiphenylamine-based antioxidants such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine; polyalkyldiphenylamine-based antioxidants such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine; naphthylamine-based antioxidants such as ⁇ -naphthylamine, and phenyl
  • antioxidant (E) one alone may be used or two or more kinds may be used in combination.
  • a mixture of one or more kinds of phenol-based antioxidants and one or more kinds of amine-based antioxidants is preferred.
  • the content of the antioxidant (E) may be appropriately controlled within a range not detracting from wear resistance, and is, based on the total amount of the lubricating oil composition, generally 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.10 to 5% by mass.
  • the lubricating oil composition of one embodiment of the present invention may contain, as needed, any other additives for a lubricating oil than the components (A) to (E) (hereinafter may be simply referred to as "lubricant additives") within a range not detracting from the advantageous effects of the present invention.
  • lubricant additives examples include a rust inhibitor, a metal deactivator, and an anti-foaming agent.
  • a compound having plural functions as the above-mentioned additives may also be used.
  • lubricant additives may be used or two or more kinds thereof may be used in combination.
  • the content of the lubricant additive may be appropriately controlled within a range not detracting from the advantageous effects of the present invention, and is, based on the total amount of the lubricating oil composition, generally 0.0005 to 15% by mass, preferably 0.001 to 10% by mass, more preferably 0.005 to 8% by mass.
  • the total content of these lubricant additives is, based on the total amount of the lubricating oil composition, preferably 0 to 40% by mass, more preferably 0 to 30% by mass, even more preferably 0 to 20% by mass, further more preferably 0 to 15% by mass.
  • the rust inhibitor includes petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenylsuccinates, and polyalcohol esters.
  • the content of the rust inhibitor is, based on the total amount of the lubricating oil composition, preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass.
  • the metal deactivator includes benzotriazole compounds, tolyltriazole compounds, thiadiazole compounds and imidazole compounds.
  • the content of the metal deactivator is, based on the total amount of the lubricating oil composition, preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass.
  • the anti-foaming agent includes silicone oils, fluorosilicone oils and fluoroalkyl ethers.
  • the content of the anti-foaming agent is, based on the total amount of the lubricating oil composition, preferably 0.01 to 1% by mass, more preferably 0.02 to 0.5% by mass.
  • the lubricating oil composition of one embodiment of the present invention includes a step of blending a base oil, a thiophosphate compound (A) represented by the above-mentioned general formula (I) and a molybdenum-based compound (B).
  • a phosphate compound (C) not containing a sulfur atom, a sulfur-based compound (D) having 2 or more sulfur atoms in the molecule and not containing a phosphorus atom, an antioxidant (E), and the above-mentioned lubricant additives may be blended.
  • the blending amount of the components (A) to (D) is so controlled as to fall within the above-mentioned content range based on the total amount of the resultant lubricating oil composition, and the same shall apply to the other components.
  • the components are stirred and uniformly mixed according to a known method.
  • a lubricating oil composition in which a part of the components have denatured after blending or two components have reacted with each other to form a different component also belongs to the technical scope of the present invention.
  • the kinematic viscosity at 40°C of the lubricating oil composition of one embodiment of the present invention is, from the viewpoint of lubricity, cooling performance and reduction in friction loss during stirring, preferably 40 mm 2 /s or more.
  • the kinematic viscosity at 40°C of the lubricating oil composition of one embodiment of the present invention is preferably 40 mm 2 /s or more and 1650 mm 2 /s or less, more preferably 50 mm 2 /s or more and 1500 mm 2 /s or less, even more preferably 60 mm 2 /s or more and 1200 mm 2 /s or less, further more preferably 70 mm 2 /s or more and 1100 mm 2 /s or less.
  • the viscosity index of the lubricating oil composition of one embodiment of the present invention is, from the viewpoint of suppressing viscosity change with temperature change, preferably 60 or more, more preferably 70 or more, even more preferably 80 or more, further more preferably 90 or more, and especially preferably 100 or more.
  • the content of the component (B) in terms of molybdenum atom (Mo-equivalent) is, based on the total amount of the lubricating oil composition, preferably 150 ppm by mass or more and 3,000 ppm by mass or less, more preferably 170 ppm by mass or more and 2,500 ppm by mass or less, even more preferably 200 ppm by mass or more and 2,000 ppm by mass or less, further more preferably 220 ppm by mass or more and 1,000 ppm by mass or less, and especially preferably 270 ppm by mass or more and 400 ppm by mass or less.
  • a lubricating oil composition can be provided which can have a low friction coefficient and have excellent wear resistance in a wide range of contact pressures ranging from high to low to such an extent that the composition can resist to lubrication conditions required for precision reduction gears to be incorporated in joint sites of industrial robots that are given an extremely large load and are readily worn to form wear debris.
  • phosphorus (P) content is, based on the total amount of the lubricating oil composition, preferably 200 ppm by mass or more, more preferably 250 ppm or more and 1,000 ppm by mass or less, even more preferably 300 ppm by mass or more and 900 ppm by mass or less, further more preferably 400 ppm by mass or more and 800 ppm by mass or less, and especially preferably 400 ppm by mass or more and 620 ppm by mass or less.
  • the phosphorus atom-containing compound includes the thiophosphate compound of the above-mentioned component (A) and the phosphate compound of the component (C).
  • sulfur (S) content is, based on the total amount of the lubricating oil composition, preferably 300 ppm by mass or more, more preferably 350 ppm by mass or more and 2,000 ppm by mass or less, even more preferably 400 ppm by mass or more and 1,800 ppm by mass or less, further more preferably 500 ppm by mass or more and 1,600 ppm by mass or less, and especially preferably 720 ppm by mass or more and 1,460 ppm by mass or less.
  • a lubricating oil composition can be provided which can have more excellent wear resistance in a wide range of contact pressures ranging from high to low to such an extent that the composition can resist to lubrication conditions required for precision reduction gears to be incorporated in joint sites of industrial robots that are given an extremely large load and are readily worn to form wear debris.
  • Examples of the sulfur atom-containing compound include the thiophosphate compounds of the above-mentioned component (A) and the sulfur-based compounds of the component (D).
  • the lubricating oil composition of one embodiment of the present invention has a low friction coefficient and has excellent wear resistance in a wide range of contact pressures ranging from high to low to such an extent that the composition can resist to lubrication conditions required for precision reduction gears to be incorporated in joint sites of industrial robots that are given an extremely large load and are readily worn to form wear debris, and therefore the lubricating oil composition can be favorably used in precision reduction gears to be incorporated in joint sites of industrial robots that are given an extremely large load and are readily worn to form wear debris,
  • the precision reduction gear of one embodiment of the present invention is a precision reduction gear using the lubricating oil composition of one embodiment of the present invention. Even when wear debris is mixed in the lubricating oil composition used in the precision reduction gear of one embodiment of the present invention, the lubricating oil composition can be exchanged without disassembling the precision reduction gear, and therefore, when the precision reduction gear is incorporated in joint sites of industrial robots, the maintenance performance thereof can be improved as compared with that using grease.
  • the precision reduction gear of one embodiment of the present invention is preferably used in industrial robots.
  • the precision reduction gear of one embodiment of the present invention includes a differential gear reducer such as an oscillating reduction gear, a wavy reduction gear, and an impulse reduction gear.
  • a differential gear reducer such as an oscillating reduction gear, a wavy reduction gear, and an impulse reduction gear.
  • Cyclo (registered trademark) reduction gear by Sumitomo Heavy Industries, Ltd. RV reduction gear by Nabtesco Corporation
  • Harmonic Drive (registered trademark) by Harmonic Drive Systems Inc. etc.
  • the precision reduction gear of one embodiment of the present invention is used in a field that requires low backflush for precision positioning accuracy such as joint sites of robots, automatic tool exchangers in working machines, blade angle-adjusting pitch derives in wind-driven generators, and roll Yaw drives.
  • Components shown in Table 1 were blended to prepare lubricating oil composition in such a manner that the molybdenum, phosphorus and sulfur atom content therein, based on the total amount of the lubricating oil composition, could be as shown in Table 1 (% by mass, ppm by mass).
  • the properties of the compositions are shown in Table 1. Details of the components are mentioned below.
  • the content of each component (% by mass) shown in Table 1 is the content thereof as a dispersion containing the mineral oil.
  • Phosphate compound (C1) mixture of mono-t-butylphenyldiphenyl phosphate and di-t-butylphenylphenyl phosphate
  • Dithiocarbamate compound (D1) methylenebis(dibutyldithiocarbamate)
  • the dithiocarbamate compound (D1) was given a rating of 2 in a copper corrosion test (JIS K 2513) where the compound was added to the base oil used in the lubricating oil composition in an amount of 1% by mass and tested under the measurement condition of 100°C for 3 hours.
  • the lubricating oil compositions shown in Table 1 were so controlled that the viscosity thereof could satisfy VG100 of the ISO viscosity grade.
  • the lubricating oil compositions shown in Table 1 were so controlled that the viscosity index thereof could be 160 to 240.
  • the properties of the base oils, the constituent components and the lubricating oil compositions were measured according to the following methods.
  • the content of molybdenum atom and phosphorus atom was measured according to JPI-5S-38-03, and the content of sulfur atom was measured according to JIS K2541-6.
  • the lubricating oil compositions of Examples 1 to 5 and Comparative Examples 3 and 7 were tested in a friction test under the condition mentioned below to measure the friction coefficient thereof in 120 minutes after the start of the test, and in addition, the wear mark expansion on the ball was measured in the X (lateral) direction and the Y (longitudinal) direction using a microscope. The data were averaged to give a wear mark diameter (mm). A smaller value means more excellent wear resistance.
  • Examples 1 to 5 had a small wear mark width and had excellent wear resistance as compared with Comparative Examples 1 to 7.
  • Examples 1 to 5 had a low friction coefficient, and the fluctuation in the friction coefficient in the test (1) and the test (2) (namely, the fluctuation in the friction coefficient in a wide range of contact pressures ranging from high to low) was small.
  • the contact pressure may greatly vary depending on the application site, and therefore a lubricating oil composition whose friction coefficient fluctuation depending on contact pressures is small can be used in a wide range and is excellent in handleability.
  • Examples 4 and 5 contained the component (C1) and the component (D1), and therefore, it is known that, in these, the friction mark width and the friction mark diameter were further small and the wear resistance improved.
  • Examples 1 to 5 are that the lubricating oil compositions had excellent wear resistance and had a low friction coefficient in a wide range of contact pressures ranging from high to low.
  • the present invention can provide a lubricating oil composition which has a low friction coefficient and has excellent wear resistance in a wide range of contact pressures ranging from high to low to such an extent that the composition can resist to lubrication conditions required for precision reduction gears to be incorporated in joint sites of industrial robots that are given an extremely large load and are readily worn to form wear debris.
  • the precision reduction gear of the present invention is a precision reduction gear that uses a lubricating oil composition having a low friction coefficient and excellent in wear resistance, and therefore, even when wear debris is mixed in the lubricating oil composition, the lubricating oil composition can be exchanged without disassembling the precision reduction gear, that is, the maintenance performance of the precision reduction gear using the lubricating oil composition of the present invention is better than a case using grease, and consequently, the precision reduction gear of the present invention is useful for industrial robots.

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CN1673321A (zh) * 2004-03-24 2005-09-28 中国石油天然气股份有限公司 用加氢油制备汽车自动传动液
US20080058235A1 (en) * 2004-03-25 2008-03-06 Katsuya Takigawa Lubricative Composition for Industrial Machinery and Equipment
CN1962835B (zh) * 2005-11-08 2010-05-05 中国石油化工股份有限公司 一种开式齿轮油组合物
JP2009029891A (ja) * 2007-07-26 2009-02-12 Ntn Corp 潤滑油組成物および転がり軸受
JP2010537001A (ja) * 2007-08-24 2010-12-02 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 潤滑油組成物
JP5502356B2 (ja) 2009-03-27 2014-05-28 出光興産株式会社 ギヤ油組成物
FR2961823B1 (fr) * 2010-06-25 2013-06-14 Total Raffinage Marketing Compositions lubrifiantes pour transmissions automobiles
US9410106B2 (en) 2012-03-12 2016-08-09 Idemitsu Kosan Co., Ltd. Lubricating oil composition
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JP2015105289A (ja) 2013-11-28 2015-06-08 住鉱潤滑剤株式会社 工業用ギヤ油組成物
CN103695082A (zh) 2013-11-29 2014-04-02 青岛科润塑料机械有限公司 一种润滑油添加剂
CN104974825A (zh) 2015-06-26 2015-10-14 青岛文晟汽车零部件有限公司 一种环保型润滑油添加剂

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3872153A4 (fr) * 2018-10-23 2022-08-03 Idemitsu Kosan Co., Ltd. Composition d'huile lubrifiante, dispositif mécanique équipé d'une composition d'huile lubrifiante et procédé de production d'une composition d'huile lubrifiante

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JPWO2017171019A1 (ja) 2019-02-14
CN108884407A (zh) 2018-11-23
WO2017171019A1 (fr) 2017-10-05
EP3438233A4 (fr) 2019-11-27
JP6799585B2 (ja) 2020-12-16
US20190106647A1 (en) 2019-04-11
EP3438233B1 (fr) 2022-05-04
US10800991B2 (en) 2020-10-13

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